Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A. This journal is The Royal Society of Chemistry 2016 Electronic Supplementary Information Mesoporous C-coated SnO x nanosheets on copper foil as flexible and binder-free anodes for superior sodium-ion batteries Haidong Bian a,b, Xufen Xiao a, Shanshan Zeng a,c, Muk-Fung Yuen a,c, Zebiao Li c, Wenpei Kang a,c, Denis Y.W.Yu a, Zhengtao Xu b, *, Jian Lu d,e, Yang Yang Li a,c,f, *
Figure S1. SEM images of the as-anodized tin foils treated in a glycerol (containing 3 vol.% H 2 O) solution of 0.1 M NH 4 F and 0.1 M H 2 C 2 O 4 at 5 V for different time durations: a) 10 min, b) 20 min, c) 30 min, d) 60 min, showing the growth process of the self-assembled anodic tin(ii) acetate (SnC 4 H 6 O 4 ) nanosheets. It was observed that particles were first randomly formed and scattered on the surface after 10 min s anodization, which then became a continuous film at 20 min. Rectangular nanosheets of ~ 500 nm wide were observed at 30 min, which grew into a self-assembled nanosheets array at 60 min. The nucleation and growth of the anodic nanostructures observed here (in the glycerol electrolyte system) is similar to that observed in the ethylene glycol system previously reported by us.[1]
a 1:2 b 2:3 c d 1:1 3:2 e f 2:1 4:1 Figure S2. SEM images of tin substrate anodized at 5 V for 60 min in a glycerol (containing 3 vol% H 2 O) solution of 0.1 M H 2 C 2 O 4 and different concentrations of NH 4 F: a) 0.05M, b) 0.067 M, c) 0.1 M, d) 0.15 M, e) 0.2 M, and f) 0.4 M, showing the impact of the F - /C 2 O 2-4 ratio on the anodic morphology obtained. With the F - /C 2 O 2-4 ratio below 1, only granular films were obtained. By increasing the F - /C 2 O 2-4 ratio above 1:1, self-assembled rectangular nanosheets were obtained with sheet width varying ~ 2-5 μm (d-f).
a 3% H 2 O b 15% H 2 O c d 30% H 2 O 60% H 2 O Figure S3. SEM images of the tin substrate anodized at 5 V for 60 min in the glycerol (containing 3 vol% (a), 15 vol% (b), 30 vol% (c), or 60 vol% (d) H 2 O) solution of 0.1 M H 2 C 2 O 4 and 0.15 M of NH 4 F. It can be seen that larger rectangular nanosheets were obtained with higher water content in glycerol (nanosheets size of ~ 1.5 to 150 μm for H 2 O content of 3 to 60 vol%).
Figure S4. Typical current density vs. time (i-t) profile recorded for a pure Sn foil anodized at 5 V for 7200 s in a glycerol (containing 15 vol.% H 2 O) solution of 0.2 M NH 4 F and 0.1 M H 2 C 2 O 4.
Figure S5. XRD pattern of the tin(ii) acetate (SnC 4 H 6 O 4 ) nanosheets fabricated by anodization at 5 V for 3600 s in a glycerol (containing 15 vol.% H 2 O) solution of 0.2 M NH 4 F and 0.1 M H 2 C 2 O 4.
Figure S6. XRD pattern of the anodized sample after annealed at 300 o C for 2 h in Ar. The anodization was carried out at 5 V for 1800 s in a glycerol (containing 15 vol. % H 2 O) solution of 0.2 M NH 4 F and 0.1 M H 2 C 2 O 4.
Figure S7. TGA curve of the C@SnO x /Cu sample measured between 30 and 900 o C at a heating rate of 10 o C min -1 in air.
Figure S8. Raman spectra of as-fabricated SnO x /Cu and C@SnO x /Cu.
Figure S9. N 2 adsorption and desorption isotherms of porous SnO x at 77 K with the inset showing the pore-size distribution calculated using the BJH from the adsorption branch.
Figure S10. N 2 adsorption and desorption isotherms of as-prepared porous C@SnO x at 77 K. The inset shows the pore-size distribution calculated from the adsorption branch using the BJH.
Figure S11. SEM images of as-annealed porous SnO x sample (before carbon coating).
Table S1. Recent studies on SnO 2 -based materials for NIBs. Structure Reversible Charge/discharge Cycles Fabrication W/ Ref. capacity current density ( binder? (ma h g -1 ) ma g -1 ) Mesoporous SnO x 404 100 100 facile anodization N This work nanosheets Octahedral SnO 2 nanocrystals 432 20 100 hydrothermal Y [2] SnO 2 @graphene 270 100 100 ball milling Y [3] SnO 2 -RGO 330 100 150 hydrothermal SnO 2 @3DG 432 100 200 hydrothermal Y [4] Y [5] WNTs@SnO 2 @C 200 150 300 hydrothermal Y [6] Al 2 O 3 /SnO 2 /CC 375 134 100 hydrothermal and ALD A-SnO 2 /CNT 223.2 1600 300 solution-based precipitation N [7] Y [8] PCNF@SnO 2 @C 374 50 100 electrodeposition Y [9] SnO 2 @void@c 401 50 50 Precipitation and heat treatment Sn/SnO 2 /C 245 20 100 hydrothermal Y [10] Y [11] Mesoporous Sn/SnO 2 372.3 50 50 temptation Y [12] a-sno 2 /GA 380.2 50 100 hydrothermal SnO 2 NRs/G 200 20 100 hydrothermal Y [13] Y [14]
SnO 2 /C 238 50 50 hydrothermal Y [15] Mesoporous 510 100 100 facile anodization N This work C@SnO x followed by nanosheets carbonization Reference [1]. Bian, H.; Tian, Y.; Lee, C.; Yuen, M.-F.; Zhang, W.; Li, Y. Y., ACS Appl. Mat. Interfaces 2016, 8, 28862-28871. [2]. Su, D.; Wang, C.; Ahn, H.; Wang, G., PCCP 2013, 15, 12543-12550. [3]. Li, S.; Wang, Y.; Qiu, J.; Ling, M.; Wang, H.; Martens, W.; Zhang, S., RSC Adv. 2014, 4, 50148-50152. [4]. Wang, Y.-X.; Lim, Y.-G.; Park, M.-S.; Chou, S.-L.; Kim, J. H.; Liu, H.-K.; Dou, S.-X.; Kim, Y.- J., J. Mater. Chem. A 2014, 2, 529-534. [5]. Pei, L.; Jin, Q.; Zhu, Z.; Zhao, Q.; Liang, J.; Chen, J., Nano Res. 2015, 8, 184-192. [6]. Zhao, Y.; Wei, C.; Sun, S.; Wang, L. P.; Xu, Z. J., Advanced Science 2015, 2, 1500097. [7]. Liu, Y.; Fang, X.; Ge, M.; Rong, J.; Shen, C.; Zhang, A.; Enaya, H. A.; Zhou, C., Nano Energy 2015, 16, 399-407. [8]. Cui, J.; Xu, Z.-L.; Yao, S.; Huang, J.; Huang, J.-Q.; Abouali, S.; Garakani, M. A.; Ning, X.; Kim, J.-K., J. Mater. Chem. A 2016, 4, 10964-10973. [9]. Dirican, M.; Lu, Y.; Ge, Y.; Yildiz, O.; Zhang, X., ACS Appl. Mat. Interfaces 2015, 7, 18387-
18396. [10]. Li, H. Z.; Yang, L. Y.; Liu, J.; Li, S. T.; Fang, L. B.; Lu, Y. K.; Yang, H. R.; Liu, S. L.; Lei, M., J. Power Sources 2016, 324, 780-787. [11]. Cheng, Y.; Huang, J.; Li, J.; Xu, Z.; Cao, L.; Qi, H., J. Power Sources 2016, 324, 447-454. [12]. Tang, D.; Huang, Q.; Yi, R.; Dai, F.; Gordin, M. L.; Hu, S.; Chen, S.; Yu, Z.; Sohn, H.; Song, J.; Wang, D., Eur. J. Inorg. Chem. 2016, 2016, 1950-1954. [13]. Fan, L.; Li, X.; Yan, B.; Feng, J.; Xiong, D.; Li, D.; Gu, L.; Wen, Y.; Lawes, S.; Sun, X., Adv. Energy Mater. 2016, 6, 1502057. [14]. Zhu, J.; Deng, D., Chem. Eng. Sci. 2016, 154, 54-60. [15]. Lu, Y. C.; Ma, C.; Alvarado, J.; Kidera, T.; Dimov, N.; Meng, Y. S.; Okada, S., J. Power Sources 2015, 284, 287-295.